CN102912373A - Method for manufacturing composite electrode plate in titanium-cladded copper layer shape by using spray deposition method - Google Patents
Method for manufacturing composite electrode plate in titanium-cladded copper layer shape by using spray deposition method Download PDFInfo
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- CN102912373A CN102912373A CN2012104336436A CN201210433643A CN102912373A CN 102912373 A CN102912373 A CN 102912373A CN 2012104336436 A CN2012104336436 A CN 2012104336436A CN 201210433643 A CN201210433643 A CN 201210433643A CN 102912373 A CN102912373 A CN 102912373A
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- 229910052802 copper Inorganic materials 0.000 title claims abstract description 82
- 239000010949 copper Substances 0.000 title claims abstract description 82
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000009718 spray deposition Methods 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title abstract description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 122
- 239000010936 titanium Substances 0.000 claims abstract description 121
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 120
- 238000000576 coating method Methods 0.000 claims abstract description 14
- 239000011248 coating agent Substances 0.000 claims abstract description 8
- 238000003466 welding Methods 0.000 claims description 48
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 32
- 238000005097 cold rolling Methods 0.000 claims description 19
- 229910052786 argon Inorganic materials 0.000 claims description 18
- 238000005098 hot rolling Methods 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 12
- IUYOGGFTLHZHEG-UHFFFAOYSA-N copper titanium Chemical compound [Ti].[Cu] IUYOGGFTLHZHEG-UHFFFAOYSA-N 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000013049 sediment Substances 0.000 claims description 8
- 238000000889 atomisation Methods 0.000 claims description 6
- 238000001540 jet deposition Methods 0.000 claims description 6
- 238000004381 surface treatment Methods 0.000 claims description 6
- 238000007669 thermal treatment Methods 0.000 claims description 6
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 4
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 3
- 238000005096 rolling process Methods 0.000 claims description 2
- 238000005507 spraying Methods 0.000 abstract description 20
- 238000005266 casting Methods 0.000 abstract description 7
- 230000004927 fusion Effects 0.000 abstract description 7
- 239000000758 substrate Substances 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 4
- 238000010891 electric arc Methods 0.000 abstract description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000460 chlorine Substances 0.000 abstract description 3
- 229910052801 chlorine Inorganic materials 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 238000000605 extraction Methods 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract 1
- 239000007921 spray Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000007592 spray painting technique Methods 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000004699 copper complex Chemical class 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a composite electrode plate in a titanium-cladded copper layer shape used for insoluble anodes in fields of non-ferrous metal extraction, chlorine alkali industry and the like and a method for manufacturing the composite electrode plate. A composite plate in a titanium or copper layer shape with copper as an inner core and titanium cladded outside is manufactured by using a electric arc spraying method, a fusion casting method or a spray deposition method, the three methods are simple in processes, easy to operate and applicable to industrialization production; combining properties, electrical conductivity and corrosion resistance of interfaces of the manufactured composite plate in the titanium or copper layer shape are superior; and according to coating titanium anodes manufactured with the composite plate serving as a substrate, the electrode internal resistance is low, the current distribution is uniform, the product purity is high, and compared with traditional coating titanium electrodes, the cell voltage is reduced by 0.1V to 0.8 V, and accordingly, energy is saved and consumption is reduced.
Description
Patent application of the present invention is from Chinese number of patent application: 200910094554,1, and the applying date: on June 8th, 2009, denomination of invention is: " preparation method of titanium/titanium/copper laminated composite electrode plate " division comes.
Technical field
The present invention relates to the preparation method that the fields such as non-ferrous metal extraction, chlorine industry are used for insoluble anode substrate titanium/copper laminated composite plate.
Background technology
The titanium electrode extracts and the chlorine industry field because its excellent solidity to corrosion and dimensional stability are widely used in non-ferrous metal, but traditional coated titanium electrode is take titanium or titanium alloy as substrate, there are the defectives such as internal resistance is large, current efficiency is low, present research emphasis both domestic and external mainly is the research of alloy system and coating aspect, to improve the use properties of electrode, internal resistance does not significantly act on and the method is to the reduction electrode.
The corrosion resisting property that titanium/comprehensive titanium of copper stratified composite is good and the good electroconductibility of copper are applied to the titanium electrode, can improve the electroconductibility of electrode and the even distribution of electric current, thereby improve the over-all properties of electrode.
The problems such as at present, the technique of the compound comparative maturity of titanium/copper has compound, the hot rolling of blast, welding, and above-mentioned several techniques exist energy consumption large, and production cost is high, and geometric accuracy is poor, and yield rate is low.
Therefore, the preparation method who develops titanium/carbon/carbon-copper composite material that a kind of preparation technology is simple, production cost is low, energy consumption is little, material use efficiency is high, dimensional precision is high is the technical barrier that current researchist faces.The inventor has found a kind of preparation method of titanium/carbon/carbon-copper composite material through for many years fundamental research.
Summary of the invention
The objective of the invention is provides titanium/carbon/carbon-copper composite material that a kind of preparation technology is simple, production cost is low, material use efficiency is high, dimensional precision is high, conduct electricity very well and preparation method thereof for the larger problem of titanium electrode material internal resistance.
Titanium/titanium/copper laminated composite electrode plate of the present invention is characterised in that: adopt arc spraying at titanium or copper coin spraying layer of copper or titanium or adopt spray deposition jet deposition layer of copper or titanium or adopt fusion casting to water cast copper at the titanium box direct injection of making on titanium or copper coin, the rolling rear bound edge welding of thermal treatment, obtain take inner core as copper, the outer titanium copper-clad laminated composite plate that is coated by titanium, wherein the thickness of titanium layer is 0.6～1.2 ㎜.
The welding of described bound edge be in argon arc welding, union-melt weld, electron-bombardment welding, plasma arc welding, the electric-resistance seam-welding any.
Titanium/copper complex method comprises that adopting arc spraying, fusion casting or spray deposition to prepare inner core is copper, the outer laminated composite plate that is coated by titanium.
Described arc spraying is at titanium or copper coin spraying layer of copper or titanium; Described spray deposition is jet deposition layer of copper or titanium on titanium or copper coin; Described fusion casting is watered cast copper at the titanium box direct injection of making.
The concrete steps of described arc spraying are: with copper coin deoil, surface treatment, utilize arc-spraying machine spray coating one deck titanium, then under 500～900 ℃, carry out hot rolling, cold rolling, make titanium copper-clad composition board; Or with the titanium plate deoil, surface treatment, sandblast, erosion, utilize arc-spraying machine to spray certain thickness copper layer at a face of titanium plate, gained covers copper titanium plate and carry out hot rolling under 400～850 ℃, and is rear cold rolling, get composite board of titanium/copper, again with behind the copper face coated copper welding compound, two titanium copper composition board copper face superimposions, thermal treatment, a kind of bound edge welding by in argon arc welding, union-melt weld, electron-bombardment welding, plasma arc welding, the electric-resistance seam-welding makes titanium copper-clad composition board.Above-mentioned two kinds of methods make titanium copper-clad composition board after the surface treatment coating, namely make to produce to use titanium anode plate.
The preparation process of described spray deposition is: copper coin is deoiled, and sandblast is preheated to 300～700 ℃, sends into vacuum or argon atmospher sediment chamber, and is cold rolling 500～900 ℃ of lower hot rollings by pressure atomization double-sided deposition one deck titanium, makes titanium copper-clad composition board; Or the titanium plate deoiled, sandblast, preheating temperature is 300～800 ℃, send into vacuum or argon atmospher sediment chamber, by the face jet deposition layer of copper of pressure atomization shower nozzle at the titanium plate, under 400～850 ℃, carry out afterwards hot rolling, cold rolling, make composite board of titanium/copper, again with behind the copper face coated copper welding compound, two titanium copper composition board copper face superimposions, thermal treatment, a kind of bound edge welding by in argon arc welding, union-melt weld, electron-bombardment welding, plasma arc welding, the electric-resistance seam-welding makes titanium copper-clad composition board.Above-mentioned two kinds of methods make titanium copper-clad composition board after the surface treatment coating, namely make to produce to use titanium anode plate.
The concrete steps of described fusion casting are: the titanium plate is deoiled, sandblast, cleans up, be prepared into the titanium box by melting, flash welding, argon arc welding, union-melt weld, electron beam welding, plasma arc welding or resistance welding, be preheated to 300～800 ℃, copper Implanted Titanium box with 1100～1300 ℃ of molten states, under 300～800 ℃ of temperature, carry out hot rolling subsequently, cold rolling, be prepared into titanium copper-clad composition board.
Described spraying or copper layer thickness are that 0.5～1.0 ㎜, titanium layer thickness are 0.8～1.2 ㎜.
Described titanium can be pure titanium or titanium alloy, and copper can be fine copper or copper alloy.
Titanium of the present invention/copper compounding technology comprises that adopting arc spraying, fusion casting or spray deposition to prepare inner core is copper, the outer titanium that is coated by titanium/copper laminated composite plate, is specifically described as follows:
(1) to prepare titanium/copper (titanium copper-clad) composition board step as follows in electric arc spraying:
With the titanium plate deoil, sandblast, utilize the thick copper layer of arc-spraying machine spraying one deck 0.5～1.0 ㎜, gained covers copper titanium plate and carry out hot rolling under 300～800 ℃, cold rolling afterwards, make the titanium copper composition board, the electric arc spraying process parameter is arc voltage 32～42V, working current 160～200A, air pressure 0.3～0.9MPa, spray distance 80～200 ㎜.
Copper coin is deoiled, sandblast, cleans up, utilize the thick titanium layer of arc-spraying machine double-face spray painting one deck 0.8～1.2 ㎜, under 500～900 ℃, carry out hot rolling, cold rolling afterwards, make titanium copper-clad composition board, the electric arc spraying process parameter is arc voltage 32～42V, working current 160～200A, air pressure 0.3～0.9MPa, spray distance 80～200 ㎜.
(2) to prepare titanium/copper (titanium copper-clad) composition board step as follows for jet deposition:
The titanium plate is deoiled, sandblast, cleans up, and preheating temperature is 400～800 ℃, sends into vacuum or argon atmospher sediment chamber, by pressure atomization shower nozzle deposition one deck 0.5～1.0 ㎜ copper layer, carries out hot rolling under 300～800 ℃, and is rear cold rolling, makes composite board of titanium/copper.
With copper coin deoil, sandblast, cleaning, preheating temperature is 300～800 ℃, sends into vacuum or argon atmospher sediment chamber, by pressure atomization shower nozzle double-sided deposition 0.8～1.2 ㎜ titanium layer, carries out hot rolling under 300～800 ℃, and is rear cold rolling, makes titanium copper-clad composition board.
The titanium plate thickness is 0.8～1.2 ㎜ in aforesaid method (1) and (2), and copper plate thickness is 0.6～1.5 ㎜.
Obtained titanium copper composition board in aforesaid method (1) and (2), copper face coated copper welding compound, rear two titanium copper composition board copper face superimposions, thermal treatment, a kind of bound edge welding by in argon arc welding, union-melt weld, electron-bombardment welding, plasma arc welding, the electric-resistance seam-welding makes titanium copper-clad composition board.
(3) to prepare titanium copper-clad matrix material step as follows for fusion casting:
The titanium plate is deoiled, sandblast, cleans up, be prepared into the titanium box by melting, flash welding, argon arc welding, union-melt weld, electron beam welding, plasma arc welding, resistance welding, be preheated to 300～800 ℃, copper Implanted Titanium box with 1100～1300 ℃ of molten states, under 300～800 ℃ of temperature, carry out hot rolling subsequently, cold rolling, be prepared into titanium copper-clad composition board.
Described titanium copper-clad composition board is preparation titanium electrode substrate used thereof, carries out surface treatment, coating, makes to produce and uses titanium anode plate.
Above-mentioned all titaniums, copper can be fine copper, pure titanium, or copper alloy, titanium alloy.
Preparation technology of the present invention is simple, easy to operate, adapt to industrialization production, prepared titanium/copper laminated composite plate interfacial bonding property, electroconductibility, corrosion resistance excellent, with it as the prepared coating titanium anode of substrate, make electrode internal resistance reduction, distribution of current is even, product purity is high, bath voltage is compared with conventional coatings titanium electrode and is reduced by 0.1～0.8V, thereby reaches energy-saving and cost-reducing effect.
Description of drawings
(a) is compound section figure for the composite board of titanium/copper part sectioned view reaches (b) among Fig. 1.
(a) is titanium copper-clad composite plate structure synoptic diagram and (b) for part sectioned view among Fig. 2.
Fig. 3 is titanium box structural representation.
Embodiment
The below further specifies flesh and blood of the present invention with example, but content of the present invention is not limited to this.
Embodiment 3 deoils 120 * 120 * 0.8 ㎜ titanium plate surface, sandblast, clean up, and puts into the argon atmospher sediment chamber, is preheated to 500 ℃ of copper layers that spray deposition 0.6 ㎜ is thick, under 500 ℃ of temperature, carry out hot rolling, rear cold rolling, make the titanium copper composition board, copper face applies the layer of copper welding compound, stack applies certain pressure, and insulation is 60 minutes in 600 ℃ of process furnace, and is cold rolling, weld with the argon arc welding bound edge, make titanium copper-clad composition board, coatings applications, bath voltage reduces 0.2V.
Embodiment 4 deoils 100 * 100 * 1.0 ㎜ copper coin surfaces, sandblast, clean up, and puts into the argon atmospher sediment chamber, is preheated to 700 ℃ of thick titanium layers of two-sided spray deposition 1.0 ㎜, under 900 ℃ of temperature, carry out hot rolling, rear cold rolling, make titanium copper-clad composition board, coatings applications, bath voltage reduces 0.4V.
Deoil in the titanium plate surface that embodiment 5 is thick with 0.8 ㎜, sandblast, clean up, be prepared into the titanium box that physical dimension is 120 * 120 * 6 ㎜ by argon arc welding, be preheated to 500 ℃, 1200 ℃ of molten state copper are injected box, after carry out 600 ℃ hot rolling, cold rolling, be prepared into titanium copper-clad composition board, coatings applications, bath voltage reduces 0.3V.
Claims (3)
1. a spray deposition prepares the method for titanium copper-clad layered composite electrode plate, it is characterized in that adopting spray deposition jet deposition layer of copper or titanium on titanium or copper coin, the rolling rear bound edge welding of thermal treatment, obtaining inner core is copper, the outer titanium copper-clad laminated composite plate that is coated by titanium; Preparation process is:
Copper coin is deoiled, and sandblast is preheated to 300～700 ℃, sends into vacuum or argon atmospher sediment chamber, and is cold rolling 500～900 ℃ of lower hot rollings by pressure atomization double-sided deposition one deck titanium, makes titanium copper-clad composition board;
Or the titanium plate deoiled, sandblast, preheating temperature is 300～800 ℃, sends into vacuum or argon atmospher sediment chamber, by the face jet deposition layer of copper of pressure atomization shower nozzle at the titanium plate, carries out afterwards hot rolling under 400～850 ℃, and is cold rolling, makes the composition board of titanium copper-clad,
Again with behind the copper face coated copper welding compound, two titanium copper composition board copper face superimposions, thermal treatment by a kind of bound edge welding in argon arc welding, union-melt weld, electron-bombardment welding, plasma arc welding, the electric-resistance seam-welding, makes the composition board of titanium copper-clad;
Above-mentioned two kinds of methods make titanium copper-clad composition board after the surface treatment coating, namely make to produce with titanium copper-clad laminated composite plate, and wherein the thickness of copper layer is 0.5～1.0 ㎜, and the thickness of titanium layer is 0.6～1.2 ㎜.
2. spray deposition according to claim 1 prepares the method for titanium copper-clad layered composite electrode plate, it is characterized in that: described titanium layer thickness is 0.8～1.2 ㎜.
3. the preparation method of titanium/titanium/copper laminated composite electrode plate according to claim 1, it is characterized in that: described titanium is pure titanium or titanium alloy, copper is fine copper or copper alloy.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210433643.6A CN102912373B (en) | 2009-06-08 | 2009-06-08 | Spray deposition prepares the method for titanium bag titanium/copper laminated composite electrode plate |
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| CN201210433643.6A CN102912373B (en) | 2009-06-08 | 2009-06-08 | Spray deposition prepares the method for titanium bag titanium/copper laminated composite electrode plate |
| CNA2009100945541A CN101575714A (en) | 2009-06-08 | 2009-06-08 | Titanium/copper laminated composite electrode plate and preparation method thereof |
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| CNA2009100945541A Division CN101575714A (en) | 2009-06-08 | 2009-06-08 | Titanium/copper laminated composite electrode plate and preparation method thereof |
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| CN102912373A true CN102912373A (en) | 2013-02-06 |
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| CN201210433643.6A Expired - Fee Related CN102912373B (en) | 2009-06-08 | 2009-06-08 | Spray deposition prepares the method for titanium bag titanium/copper laminated composite electrode plate |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103668318A (en) * | 2009-06-08 | 2014-03-26 | 昆明理工大学 | Method for preparing titanium-clad copper layered composite electrode plate by spray deposition method |
| TWI569900B (en) * | 2016-06-30 | 2017-02-11 | 中國鋼鐵股份有限公司 | Method of fabricating titanium-clad-copper electrode |
| CN109088184A (en) * | 2017-06-14 | 2018-12-25 | 深圳华淮新材料有限公司 | A kind of titanium packet aluminum alloy corrosion resistant earthing material |
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| CN102433573B (en) * | 2011-11-17 | 2014-11-12 | 常州大学 | Titanium-lead composite anode and preparation method thereof |
| CN102601153B (en) * | 2012-03-14 | 2014-09-10 | 河海大学 | Method for preparing layered nickel/aluminum composite material |
| CN104028603A (en) * | 2014-05-29 | 2014-09-10 | 哈尔滨理工大学 | Heterogeneous material tailor-welded blank hot stamping forming device and method with controllable temperature field |
| CN106158288B (en) * | 2016-06-22 | 2019-12-06 | 西北核技术研究所 | Copper-titanium composite Tesla transformer primary coil |
| CN111055036B (en) * | 2019-11-28 | 2021-04-30 | 上海微电子装备（集团）股份有限公司 | Metal additive manufacturing method |
| CN112872735B (en) * | 2021-01-19 | 2022-03-11 | 西部金属材料股份有限公司 | Preparation method of titanium alloy H-shaped material |
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- 2009-06-08 CN CNA2009100945541A patent/CN101575714A/en active Pending
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103668318A (en) * | 2009-06-08 | 2014-03-26 | 昆明理工大学 | Method for preparing titanium-clad copper layered composite electrode plate by spray deposition method |
| CN103668318B (en) * | 2009-06-08 | 2017-01-04 | 昆明理工大学 | Spray deposition prepares the method for titanium bag titanium/copper laminated composite electrode plate |
| TWI569900B (en) * | 2016-06-30 | 2017-02-11 | 中國鋼鐵股份有限公司 | Method of fabricating titanium-clad-copper electrode |
| CN109088184A (en) * | 2017-06-14 | 2018-12-25 | 深圳华淮新材料有限公司 | A kind of titanium packet aluminum alloy corrosion resistant earthing material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102912373B (en) | 2016-03-02 |
| CN101575714A (en) | 2009-11-11 |
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